TY - JOUR
T1 - Development of Shape-Tuned, Monodisperse Block Copolymer Particles through Solvent-Mediated Particle Restructuring
AU - Shin, Jae Man
AU - Lee, Young Jun
AU - Kim, Mingoo
AU - Ku, Kang Hee
AU - Lee, Junhyuk
AU - Kim, Yongjoo
AU - Yun, Hongseok
AU - Liao, Kin
AU - Hawker, Craig J.
AU - Kim, Bumjoon J.
N1 - Funding Information:
This work was supported by the Agency for Defense Development of the Republic of Korea, under the contract number UD160085BD. This research was supported by the Korea Research Foundation Grant, funded by the Korean Government (2012M3A6A7055540 and 2017M3D1A1039553). C.J.H acknowledges support from the National Science Foundation, Division of Materials Research under the Materials Research Science & Engineering Centers Program (UCSB MRSEC and NSF DMR 1720256). The authors also acknowledge additional support for this work from the Research Project of the KAIST-KUSTAR.
Publisher Copyright:
© Copyright 2019 American Chemical Society.
PY - 2019/2/12
Y1 - 2019/2/12
N2 - Control of the shape, size, internal structure, and uniformity of block copolymer (BCP) particles is crucial for determining their utility and functionality in practical applications. Here, we demonstrate a particle restructuring by solvent engineering (PRSE) strategy that combines membrane emulsification and solvent annealing processes to produce monodisperse BCP particles with controlled size, shape, and internal structure. A major advantage of the PRSE approach is the general applicability to different families of functional BCPs, including polystyrene-block-poly(1,4-butadiene) (PS-b-PB), polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS), and polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP). PRSE starts with the production of monodisperse BCP spheres in a wide range of particle sizes (from hundreds of nanometers to several tens of microns) using membrane emulsification, followed by successful transformation to shape-anisotropic BCP particles by solvent annealing under neutral wetting conditions. Particle size monodispersity was maintained during the PRSE process with shape transformations from sphere to ellipsoids (i.e., oblate and prolate). The approach was effective in controlling the aspect ratio (AR) of both prolate and oblate ellipsoids over wide ranges. These ARs were well-supported by free energy calculations based on a theoretical model describing particle elongation. Further investigation of the shape-transformation kinetics during the PRSE process revealed that the morphology transformation was driven by reorientation of BCP microdomains, with kinetics being strongly associated with the overall molecular weight of the BCP as well as the annealing time.
AB - Control of the shape, size, internal structure, and uniformity of block copolymer (BCP) particles is crucial for determining their utility and functionality in practical applications. Here, we demonstrate a particle restructuring by solvent engineering (PRSE) strategy that combines membrane emulsification and solvent annealing processes to produce monodisperse BCP particles with controlled size, shape, and internal structure. A major advantage of the PRSE approach is the general applicability to different families of functional BCPs, including polystyrene-block-poly(1,4-butadiene) (PS-b-PB), polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS), and polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP). PRSE starts with the production of monodisperse BCP spheres in a wide range of particle sizes (from hundreds of nanometers to several tens of microns) using membrane emulsification, followed by successful transformation to shape-anisotropic BCP particles by solvent annealing under neutral wetting conditions. Particle size monodispersity was maintained during the PRSE process with shape transformations from sphere to ellipsoids (i.e., oblate and prolate). The approach was effective in controlling the aspect ratio (AR) of both prolate and oblate ellipsoids over wide ranges. These ARs were well-supported by free energy calculations based on a theoretical model describing particle elongation. Further investigation of the shape-transformation kinetics during the PRSE process revealed that the morphology transformation was driven by reorientation of BCP microdomains, with kinetics being strongly associated with the overall molecular weight of the BCP as well as the annealing time.
UR - http://www.scopus.com/inward/record.url?scp=85060533526&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.8b04777
DO - 10.1021/acs.chemmater.8b04777
M3 - Article
AN - SCOPUS:85060533526
SN - 0897-4756
VL - 31
SP - 1066
EP - 1074
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 3
ER -